Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam, The Netherlands.
J Am Chem Soc. 2011 Nov 2;133(43):17176-9. doi: 10.1021/ja208589c. Epub 2011 Oct 11.
We report an achiral bisphosphine rhodium complex equipped with a binding site for the recognition of chiral anion guests. Upon binding small chiral guests--cofactors--the rhodium complex becomes chiral and can thus be used for asymmetric catalysis. Screening of a library of cofactors revealed that the best cofactors lead to hydrogenation catalysts that form the products with high enantioselectivity (ee's up to 99%). Interestingly, a competition experiment shows that even in a mixture of 12 cofactors high ee is obtained, indicating that the complex based on the best cofactor dominates the catalysis.
我们报告了一种手性双膦配体铑配合物,其配备了一个用于识别手性阴离子客体的结合位点。当与小分子手性客体(辅因子)结合时,铑配合物变得手性,并因此可用于不对称催化。对辅因子库的筛选表明,最好的辅因子导致形成具有高对映选择性(ee 值高达 99%)的产物的氢化催化剂。有趣的是,竞争实验表明,即使在 12 种辅因子的混合物中也能获得高 ee 值,这表明基于最佳辅因子的配合物主导了催化。